The optimized geometries at the RHF/6-311++G** level, the relatively stable energy at the MPW1PW91/6-311++G** level and the structural characters of anions have been acquired, indicating the stability is related to ...The optimized geometries at the RHF/6-311++G** level, the relatively stable energy at the MPW1PW91/6-311++G** level and the structural characters of anions have been acquired, indicating the stability is related to the chemical bonding of μ2?P atoms and the distri- bution of negative charges. The configurations of cage units P8 4- and P9 5- are stable due to the less torsion, but their ES values are relatively higher than that of P7 3- with more μ2?P atoms and the isolated stability is lower than that of P7 . They potentially play an important role as intermediate 3- in chemical reaction of producing complicated polyphosphides. Based on the related electronic properties, a stable polyanion must have low valence electron concentration, no (μ2?P)?(μ2?P) bond and a little dispersive charge. The earmark IR frequencies of cage units have been assigned to the vibration models in the end.展开更多
As an improvement on the conventional two-layer electrode （active material layerlcurrent collector）, a novel sandwich-like three-layer electrode （conductive layerlactive material layertcurrent collector） for catho...As an improvement on the conventional two-layer electrode （active material layerlcurrent collector）, a novel sandwich-like three-layer electrode （conductive layerlactive material layertcurrent collector） for cathode material LiFePO4/C was introduced in order to improve its electrochemical performance. LiFePO4/C in the three-layer electrode exhibited superior rate capability in comparison with that in the two-layer electrode in accordance with charge-discharge examination. Cyclic voltammetry and electrochemical impedance spectroscopy indicated that Fe3＋/Fe2＋ redox couple for LiFePO4 in the three-layer electrode displayed faster kinetics, better reversibility and much lower charge transfer resistance than that in the two-layer electrode in electrochemical process. For three-layer electrode, the holes in the surface of active material layer were filled by smaller acetylene black grains, which formed electrical connections and provided more pathways to electron transport to/from LiFePO4/C particles exposed to the bulk electrolyte.展开更多
文摘The optimized geometries at the RHF/6-311++G** level, the relatively stable energy at the MPW1PW91/6-311++G** level and the structural characters of anions have been acquired, indicating the stability is related to the chemical bonding of μ2?P atoms and the distri- bution of negative charges. The configurations of cage units P8 4- and P9 5- are stable due to the less torsion, but their ES values are relatively higher than that of P7 3- with more μ2?P atoms and the isolated stability is lower than that of P7 . They potentially play an important role as intermediate 3- in chemical reaction of producing complicated polyphosphides. Based on the related electronic properties, a stable polyanion must have low valence electron concentration, no (μ2?P)?(μ2?P) bond and a little dispersive charge. The earmark IR frequencies of cage units have been assigned to the vibration models in the end.
基金Project(2010ZCO51)supported by Natural Science Foundation of Yunnan ProvinceProject supported by Analysis and Testing Foundation(2009-041)Starting Research Fund(14118245)from Kunming University of Science and Technology
文摘As an improvement on the conventional two-layer electrode （active material layerlcurrent collector）, a novel sandwich-like three-layer electrode （conductive layerlactive material layertcurrent collector） for cathode material LiFePO4/C was introduced in order to improve its electrochemical performance. LiFePO4/C in the three-layer electrode exhibited superior rate capability in comparison with that in the two-layer electrode in accordance with charge-discharge examination. Cyclic voltammetry and electrochemical impedance spectroscopy indicated that Fe3＋/Fe2＋ redox couple for LiFePO4 in the three-layer electrode displayed faster kinetics, better reversibility and much lower charge transfer resistance than that in the two-layer electrode in electrochemical process. For three-layer electrode, the holes in the surface of active material layer were filled by smaller acetylene black grains, which formed electrical connections and provided more pathways to electron transport to/from LiFePO4/C particles exposed to the bulk electrolyte.
